N-substituted arylcarbamoyl sulfides

ABSTRACT

Compound of the formula WHEREIN R1 and R4 are individually aryl of six to 14 carbon atoms optionally substituted with alkyl groups, halogen atoms, nitro groups, alkoxy groups, alkylthio groups or dialkylamino groups; R2 and R3 are individually hydrogen or alkyl of one to four carbon atoms. The compounds are insecticides.

United States Patent Brown, deceased 51 July 25,1972

N-SUBSTITUTED ARYLCARBAMOYL SULFIDES Appl. No.: 88,105

U.S. Cl ..260/479 C, 260/294.8 C, 260/3322 R,

260/347.2, 424/300 Int. Cl ..C07c 125/06 Field of Search ..260/479 CReferences Cited UNITED STATES PATENTS Flory et al ..260/479 PrimaryExaminer-James A. Patten Anorney-A. L. Snow, Frank E. Johnston, G. F.Mag deburger, John Stoner, Jr. and Dix A. Newell [57] ABSTRACT Compoundof the formula Raoul,

wherein R and R are individually aryl of six to l4 carbon atomsoptionally substituted with alkyl groups, halogen atoms, nitro groups,alkoxy groups, alkylthio groups or dialkylamino groups; R and R areindividually hydrogen or alkyl of one to four carbon atoms. Thecompounds are insecticides.

7 Claims, No Drawings N-SUBSTITUTED ARYLCARBAMOYL SULFIDES BACKGROUND OFTHE INVENTION Field The present invention is directed to N-substitutedaryl carbamoyl sulfides, particularly the bis-(N-substituted arylcarbamoyl) sulfides. The sulfides find use principally as insecticides.

DESCRIPTION OF THE INVENTION The N-substituted aryl carbamoyl sulfidesof the present invention may be represented by the general formula 1)it: in o l I II wherein R and R are individually aryl of six to l4carbon atoms substituted with to 4, preferably 0 to 2, halogens ofatomic number 9 to 35 (fluorine, chlorine or bromine), nitro groups,alkyl groups of one to seven carbon atoms, alkoxy groups of one to fivecarbon atoms, or alkylthio groups of one to three carbon atoms; or 0 tol dialkylamino groups in which the alkyl groups contain individually oneto three carbon atoms; R and R are individually hydrogen or alkyl of oneto four carbon atoms. Aryl" means a hydrocarbon group containing anaromatic ring or rings. The total number of substituents on the arylgroup of R or R should not exceed 4. R and R can also be a heterocyclicgroup having a heteroatom, i.e., S, N or O, in the ring. Thus, R and Rcan be thienyl, furyl, pyridyl, preferably thienyl.

R and R can be the same or different and R and R can be the same ordifferent. The preferred compounds of the present invention are thosewherein R and R are the same and R and R are the same. Thus, thepreferred compounds are the bis- N-substituted aryl carbamoyl) sulfides.

The preferred substituents for R and R are halogen atoms of atomicnumber 9 to 35 nitro groups, alkyl groups of one to seven carbon atomsor alkoxy groups of one to five carbon atoms.

Preferably R and R are individually phenyl substituted with 0 to 4halogen atoms of atomic number 9 to 35, nitro groups, alkyl groups ofone to seven carbon atoms, or alkoxy of one to five carbon atoms oralkylthio groups of one to three carbon atoms or 0 to l dialkylaminogroups in which the alkyl groups contain individually one to threecarbon atoms; or naphthyl substituted with zero to four halogen atoms ofatomic number 9 to 35, nitro groups, alkyl groups of one to four carbonatoms, alkoxy groups of one to five carbon atoms, alkylthio groups ofone to three carbon atoms or 0 to l dialkylamino groups in which thealkyl groups contain individually one to three carbon atoms. Preferablyalkyl groups substituted on the phenyl moiety will contain one to fivecarbon atoms. Still more preferably, the alkyl groups substituted on thephenyl or naphthyl moiety will contain one to four carbon atoms (of thealkyl groups, tert.butyl substituents are least preferred). Thepreferred halogen substituents on the phenyl naphthyl napthyl moietiesare chlorine or bromine, more preferably chlorine. The naphthyl moietyis preferably bonded to the carbamate oxygen either through the one" ortwo carbon atoms.

Representative aryl groups which R and R may represent include phenyl,biphenyl, naphthyl, chlorophenyl, bromophenyl, chloronaphthyl,ethylphenyl, methylphenyl, 2- chloro-4-methylphenyl, 3-chloronaphthyl,3-sec.butylphenyl, 3-sec.pentylphenyl, 2-iso-propylphenyl,4-isopropylphenyl, 3- (l-methylbutyl) phenyl, 3-( l-ethylpropyl) phenyl,3-t-amyl-6- chlorophenyl, 4-(l-ethylpropyl) phenyl, methoxyphenyl,butoxyphenyl, 2-nitrophenyl, 2-nitro-4-chlorophenyl, 4-methylthio-3-tolyl, 4-dimethylamino, 3-tolyl, etc.

R and R are preferably alkyl of one to four carbon atoms and morepreferably methyl or ethyl. Representative R and R groups include, inaddition to hydrogen, methyl and ethyl, the groups n-propyl, isopropyl,n-butyl, and isobutyl.

Furthermore, the preferred compounds of the present invention are thosewherein R and R are the same and are naphthyl, phenyl substituted with lto 2 alkyl groups of one to five carbons atoms or alkoxy groups of oneto four carbon atoms, preferably 3-alkylphenyl, 3-alkoxyphenyl,3,4-dialkylphenyl, 3,5-dialkylphenyl, the alkyl substituent being from ito 5 carbon atoms and the alkoxy group having one to four carbon atoms,and R and R are the same and are methyl groups.

Representative compounds of the present invention includebis-(phenylcarbamoyl) sulphide, bis-(2-hapthylcarbamoyl) sulfide,bis-(2-fluorophenyl-N-methylcarbamoyl) sulfide, bis-(2,4-dichlorophenyl-N-methylcarbamoyl) sulfide, bis-(3-bromophenyl-N-methylcarbamoyl) sulfide, bis-(2-chloro-4-nitrophenyl-N-ethyl-carbamoyl) sulfide, bis-( 2,3 ,4,5tetrachlorophenyl-N-methylcarbamoyl) sulfide, bis-(4-ethylphenyl-N-methylcarbamoyl) sulfide,bis-(4-methoxyphenyl-N-methylcarbamoyl) sulfide,bis-(3-chloro-4-t-butylphenyl-N-methylcarbamoyl) sulfide,bis-(4-methylthiophenyl- N-methylcarbamoyl) sulfide,bis-(4-dimethylaminophenyl-N- methyl-carbamoyl) sulfide,bis-(3,5-dibutylphenyl-N-propylcarbamoyl) sulfide,bis-(3-sec.butylphenyl-N-methylcarbamoyl) sulfide,bis-(2-chloro-4-diethylaminophenyl-N-ethylcarbamoyl) sulfide,bis-(3-butylthio-5-ethylphenyl-N-methylcarbamoyl) sulfide,bis-(2,4-dinitrophenyl-N-methylcarbamoyl sulfide,bis-(l-naphthyl-N-methylcarbamoyl) sulfide,N-(phenyl-N-methylcarbamoylthio)-N-methyl-3sec.butylphenylcarbamate.

The bis compounds of the present invention are made in accordance withthe following reaction SCI:

O R R 0 In the above equation R and R are as defined previously. It isunderstood that R and R may be written as R and R, respectively, whendiscussing the bis compounds.

The carbamate and a basic acceptor such as pyridine or triethylamine aredissolved in a suitable inert solvent such as benzene, toluene, ether,preferably a chlorinated hydrocarbon such as methylene chloride orchloroform. The temperature is maintained between approximately C. andthe boiling point of the solvent, preferably between 0 to 35 C., duringthe gradual addition of sulfur dichloride. The reaction time willgenerally be from 15 minutes to several hours, i.e., l to 2 hours.Longer reaction times do not result in degradation of the product Theamine salt is removed by water washing and the product solution dried,filtered and stripped of solvent. The product may be purified byrecrystallization, or in the case of oils by chromatography.

Unsymmetrical compounds may be prepared by reaction of 1 mole of SC],with 1 mole of a carbamate to produce an N- thiochlorocarbamate whichmay then be reacted with a different carbamate to give the unsymmetricalproduct. Reaction times and conditions, etc. are the same as that forthe preparation of the bis compound.

The carbamate reactant in the above equation may and usually willrepresent a commercial carbamate insecticide. Conventional method forpreparing such earbamates whether in situ or beforehand may be used.Such reactants are disclosed in US. Pat. Nos. 3,062,707; 3,062,864;3,062,865; 3,062,866; 2,903,478; 3,084,096; 3,208,853; 3,167,472 and3,242,145 and Pesticide Index, Third Edition, D.E.H. Frear (1965).

The preparation of the compounds of the present invention will be morefully understood by reference to the following examples.

EXAMPLE 1 A solution of 6 g. (bis-(mole) of distilled sulfur dichlorideand 10 ml. of methylene chloride was added slowly to a solution of 20.9g. (0.1 mole) of o-isopropoxyphenyl-N-methylcarbamate. The reactionmixture was stirred overnight and washed twice with 200 ml. portions ofwater, dried over magnesium sulfate, filtered and stripped. A residualoil was added to 50 ml. of benzene and approximately 1 g. of insolublesolid was removed by filtration. Following solvent removal, the residualoil was found to have an NMR spectrum compatible with the structure ofbis-(Z-isopropoxyphenyl-N-methylcarbamoyl) sulfide. The elementalanalysis of the oil was Calculated Found EXAMPLE 2 7.9 g. (0.1 mole)pyridine and 20.7 (0.l mole) of see-butylphenyl-N-methylcarbamate(actually mixed isomers containing 60 to 65 percent of the m-isomer, theresulting portion being oand p-isomers) was mixed with 100 ml. ofmethylene chloride. The solution was cooled in an ice bath while 5.2 g.(0.05 mole) of distilled pure dichloride was added slowly. The reactionmixture was stirred at ice bath temperature for 30 minutes. Then thecooling bath and stirring was continued for 2 hours at ambienttemperature. The solution was washed 2 times with 100 ml. portions ofwater, dried over magnesium sulfate and filtered. Following solventremoval under vacuum the residual oil was chromatographed on 200 ml.silica gel diluting with various mixtures of ether and hexane. The cutscontaining pure product were stripped yielding 9 g. of oil. The

elements analysis was Calculated Found N I; 6.3l 5.88 S k 7.22 8.7l

The product was bis-(N-sec.butylphenyl-N-methylcarbamoyl) sulfide (60percent was the m-isomer, the remaining portion being oand p-isomers).

Using the general procedure of Examples 1 and 2, other compounds of thisinvention were prepared. These compounds and analyses are tabulatedbelow in Table 1.

N-methylcarbamoyl) sulfide.

The compounds of the present invention find use principally asinsecticides. Some of the compounds exhibit fungicidal activity.Representative compounds of the present invention were tested as followsto illustrate the insecticidal properties. Generally the compounds arevery selective as to particular insects. The test results are reportedin Table ll.

TEST PROCEDURES Aphids (Aphis garsypii Glover):

An acetone solution of the candidate toxicant containing a small amountof nonionic emulsifier was diluted with water to 30 ppm. Cucumber leavesinfested with aphids were dipped in the toxicant solution. Mortalityreadings were then taken after 24 hours.

American Cockroach (Periplanela americana L.

A 500 ppm acetone solution of the candidate toxicant was placed in amicrosprayer (atomizer). A random mixture of anesthetized male andfemale roaches were placed in a container and 50 mg. of the abovedescribed acetone solution was sprayed on them. A lid was placed on thecontainer. A mortality reading was made after 24 hours.

Cabbage Looper (Trichoplusia ni):

An acetone solution of the candidate toxicant containing a small amountof nonionic emulsifier was diluted with water to 500 ppm. Cabbage leafsections were dipped in the toxicant solution and dried. The sectionswere then infested with cabbage looper larvae. Mortality readings weretaken after 24 hours.

Mosquito Larvae (Aedes aegypti L.

Coek Cabbage Mosquito Compound Aphids roach looper larvae Bis-[(m-sec.butylbutyl) phenyl-N -1netl1yloarbarnoyl] s J0 100llis-(3-isopr0pylphenyl-N- rnetlrylcarbamoyl) sulfide. Bis-(aurathyl-N-methylcarbamoyl sullido 60 Bis-(3,4-di1netliylplrenyl-N-mothylcurbarnoyl) sullide J0 Bis-(2-isopropoxypherryl-N-metlrylearbamoyl) sullide- 100 Primary compound-approximately 40% ol'the oand P-isomers also present.

In addition to the specific formulations and application techniquesdescribed above, one or more of the compound derivatives of theinvention may be applied in other liquid or solid formulations to theinsects, their environment, or hosts susceptible to insect attack. Forexample, they may be sprayed or otherwise applied directly to plants orsoil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxicamount of one or more compound derivatives and a biologically inertcarrier. Usually they will also contain a wetting agent. Solid carrierssuch as clay, talc, sawdust and the like may be used in suchformulations. Liquid diluents which may be used with these compoundsinclude water and arematic solvents. in addition these formulations maycontain other compatible pesticides, plant growth regulators, fillers,stabilizers, attractants and the like.

The concentrationof the active ingredient to be used with inertcarriers, either solid or liquid carriers, will be dependent upon manyfactors, such as the particular compound which is used, the carrier inor upon which it is incorporated, the method and conditions ofapplication, the insect species to be controlled, etc., the properconsideration of these factors being within the skill of those versed inthe art. In general, the toxic ingredients of this invention will beeffective in concentrations from about 0.0001 percent, by weight,preferably 0.1 weight percent, to as high as percent by weight orhigher. Economically, of course, it is desirable to use lowerconcentrations of this active ingredient. Thus, it is usually desirableto use less than 20 percent by weight of the active ingredient in aparticular composition.

The terms insecticide and insect" as used herein refer to their broadand commonly understood usage rather than to those creatures which inthe strict biological sense are classified as insects. Thus, the terminsect" is used not only to include small invertebrate animals belongingto the class Insecta but also to the other related classes of arthropodswhose members are segmented invertebrates having more or fewer than sixlegs, such as spider, mites, ticks, centipedes, worms and the like.

One of the compounds, bis-(3,5-dimethylphenyl-N-methylcarbamoyl)sulfide, was found particularly effective in the control of the fungusBotrytis cinaria. Thus using a variation of The Standard SporeSlide-Germination Method for Determining Fungicidal Activity, describedin the American Phytopathological Society Journal, Volume 33, pages627-632 (1943), the compound was tested for fungitoxic activity againstspores. The compound was dissolved in acetone to a concentration of 100ppm. The solution was then pipetted into wells of depression slides andallowed to dry. The wells were filled with a spore suspension of thetest organism Botrytis cinaria; l0-fold greater volume of suspension wasused than that used to apply the toxicant so that the slideconcentration of toxicant was about ppm. The spores were then incubatedin a moist chamber overnight. A group of 100 spores was examined and thenumber of spores germinated and not germinated was counted and recordedto show the biological activity in terms of the percent germinationinhibition. The compound bis-(3,5-dimethylphenyl-N-methylcarbamoyl)sulfide showed 98 percent inhibition.

When used as a fungicide, the compound will be formulated and applied infungicidal amounts by conventional art methods to fungi or hosts whichare subject to fungus attack, especially vegetative hosts such asplants, plant seeds, etc. The amount used will vary, of course,depending on the fungus, the host, etc. The compound may be combinedwith inert liquids or solid carriers as powders, solutions, dispersions,etc. When so combined, the compound should be in an amount of from 0.005to 95 weight percent, preferably 1 to 50 weight percent. Suitable liquidcarriers include water, kerosene, xylene, alcohols, alkylatednaphthylene and glycols. Solid carriers include kaolin clays,diatomaceous earth, silica, talc, etc.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion, without departing from the spirit or scope ofthe disclosure or from the scope of the following claims.

It is claimed:

1. Compound of the formula wherein R and R are individually aryl of sixto 14 carbon atoms substituted with 0 to 4 halogens of atomic number 9to 35 (fluorine, chlorine or bromine), nitro groups, alkyl groups of oneto seven carbon atoms, alkoxy groups of one to five carbon atoms oralkylthio groups of one to three carbon atoms; or 0 to l dialkylarninogroups in which the alkyl groups contain individually one to threecarbon atoms; R and R are individually hydrogen or alkyl of one to fourcarbon atoms.

2. Compound of claim 1 wherein R and R are the same radical and R and Rare the same radical.

3. Compound of claim 1 wherein R and R are individually phenylsubstituted with zero to four halogen atoms of atomic number 9 to 35,nitro groups, alkyl groups of one to seven carbon atoms, alkoxy groupsof one to five carbon atoms, or alkylthio groups of one to three carbonatoms; or 0 to l dialkylamino groups in which the alkyl groups containindividually one to three carbon atoms; or naphthyl substituted withzero to four halogen atoms of atomic number 9 to 35, nitro groups, alkylgroups of one to four carbon atoms, alkoxy gfiloups of one to fivecarbon atoms alkylthio groups of one to ee carbon atoms; or 0 to ldialkylammo groups in WhlCh the alkyl groups contain individually one tothree carbon atoms.

4. Compound of claim 3 wherein the alkyl groups substituted on thephenyl moiety contains one to five carbon atoms.

5. Compound of claim 1 wherein R and R are individually alkyl of one tofour carbon atoms.

6. Compound of claim 1 wherein R and R are the same and are phenylsubstituted with zero to four halogen atoms of atomic number 9 to 35,nitro groups, alkyl groups of one to seven carbon atoms or alkoxy groupsof one to five carbon atoms or naphthyl substituted with zero to fourhalogen atoms of atomic number 9 to 35, nitro groups, alkyl groups ofone to four carbon atoms or alkoxy groups of one to five carbon atomsand R and R are the same and are methyl or ethyl.

7. Compound of claim 1 wherein R and R are the same and are naphthyl,phenyl substituted with l to 2 alkyl groups of one to four carbon atomsor alkoxy groups of one to four carbon atoms, and R and R are the sameand are methyl.

2. Compound of claim 1 wherein R1 and R4 are the same radical and R2 andR3 are the same radical.
 3. Compound of claim 1 wherein R1 and R4 areindividually phenyl substituted with zero to four halogen atoms ofatomic number 9 to 35, nitro groups, alkyl groups of one to seven carbonatoms, alkoxy groups of one to five carbon atoms, or alkylthio groups ofone to three carbon atoms; or 0 to 1 dialkylamino groups in which thealkyl groups contain individually one to three carbon atoms; or naphthylsubstituted with zero to four halogen atoms of atomic number 9 to 35,nitro groups, alkyl groups of one to four carbon atoms, alkoxy groups ofone to five carbon atoms, alkylthio groups of one to three carbon atoms;or 0 to 1 dialkylamino groups in which the alkyl groups containindividually one to three carbon atoms.
 4. Compound of claim 3 whereinthe alkyl groups substituted on the phenyl moiety contains one to fivecarbon atoms.
 5. Compound of claim 1 wherein R2 and R3 are individuallyalkyl of one to four carbon atoms.
 6. Compound of claim 1 wherein R1 andR4 are the same and are phenyl substituted with zero to four halogenatoms of atomic number 9 to 35, nitro groups, alkyl groups of one toseven carbon atoms or alkoxy groups of one to five carbon aToms ornaphthyl substituted with zero to four halogen atoms of atomic number 9to 35, nitro groups, alkyl groups of one to four carbon atoms or alkoxygroups of one to five carbon atoms and R2 and R3 are the same and aremethyl or ethyl.
 7. Compound of claim 1 wherein R1 and R4 are the sameand are naphthyl, phenyl substituted with 1 to 2 alkyl groups of one tofour carbon atoms or alkoxy groups of one to four carbon atoms, and R2and R3 are the same and are methyl.